US4892856A - Catalyst for oxidation of acrolein and process for preparation thereof - Google Patents

Catalyst for oxidation of acrolein and process for preparation thereof Download PDF

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US4892856A
US4892856A US07/201,026 US20102688A US4892856A US 4892856 A US4892856 A US 4892856A US 20102688 A US20102688 A US 20102688A US 4892856 A US4892856 A US 4892856A
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Tatsuya Kawajiri
Shinichi Uchida
Masahiro Wada
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Nippon Shokubai Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8878—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size

Definitions

  • This invention relates to a catalyst suitable for the production of acrylic acid from acrolein, which comprises molybdenum and vanadium as essential components, and a process for the preparation thereof. More specifically, this invention relates to a catalyst for the oxidation of acrolein, which has high activity and excellent durability and which is characterized by specific properties, and a process for the preparation of said catalyst with ease and good reproducibility.
  • the catalyst surface areas of 0.1 to 50 m 2 /g are preferable.
  • those catalysts described therein have defects of high reaction temperatures and low level of performance.
  • Japanese Laid-Open Patent Publications Nos. 47276/1974 and 24183/1975 describe that the specific surface areas of 0.1 to 8 m 2 /g are preferable.
  • those catalysts described therein also have a defect of high reaction temperatures as high as about 300° C.
  • the definition of the pore volume and surface area it is described in Japanese Laid-Open Patent Publications Nos.
  • those catalysts described therein comprise cobalt and molybdenum as active components and they are technically on a low level.
  • Japanese Laid-Open Patent Publication No. 47590/1976 describes that a catalyst comprising phosphorus, molybdenum and thallium or an element of Group IA or II of the periodic table and formed by rolling particle-forming method so as to have a surface area of 4 to 20 m 2 /g and a pore volume of 0.08 to 0.5 ml/g has reproduction in performance.
  • this catalyst also has defects that the reaction temperature is high and the performance is unsatisfactory.
  • 9737/1982 discloses a catalyst comprising, as essential components, molybdenum, vanadium, copper, iron, manganese, alkali earth metal or zinc, and oxygen and further including phosphorus as an optional component, and a process for the production of acrylic acid by using said catalyst in the oxidation of acrolein. And it discloses an embodiment of the catalyst in which an alundum having a diameter of 3.5 mm is allowed to carry catalyst components by a rotatory sugar coater. In the catalyst therein, the reaction temperature is relatively low, i.e., about 200° C., and said catalyst achieves a high level in the yields. However, the catalyst obtained by the process has a problem in respect of reproducibility of its properties.
  • catalysts are used, in general, in the form of pellets having a suitable size. Such pellets are formed by using a tablet-forming machine, extruder, pill-forming machine, rolling particle-forming machine, etc.
  • the physical property of the resultant catalyst is not constant, that is, most cases show poor reproducibility of catalyst performance.
  • the present inventors made assiduous studies to clear up those variations of catalyst performance which are caused at the time of forming catalysts by using various forming machines.
  • Mo represents molybdenum
  • V represents vanadium
  • A represents at least one element selected from the group consisting of tungsten and niobium
  • B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony and thallium
  • C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals
  • D represents at least one element selected from the group consisting of silicon, aluminum and titanium
  • O represents oxygen
  • the pore volume composed of pores having pore diameters in the range of from 10 to less than 100 ⁇ m is not less than 10% of the entire pore volume, especially preferably, 15 to 40%, and the pore volumes composed of pores having pore diameters in the range of from 1.0 to less than 10.0 ⁇ m and pores having pore diameters in the range from 0.1 to 100 ⁇ m are not less than 10% of the entire pore volume respectively, especially preferably, 15 to 65 % respectively.
  • both of the activity and the selectivity of the above catalyst are enhanced that is, a pore having a smaller pore diameter, e.g., less than 1.0 ⁇ m, has a larger contribution toward the surface area and pore volume than pores having a larger pore diameters, e.g. larger than 0.1 ⁇ m.
  • the mere larger proportion of the smaller pores is not sufficient.
  • there is not a distribution in which pores are also distributed in two ranges of from 1.0 to less than 10.0 ⁇ m and from 10.0 to 100 ⁇ m it is not possible to obtain enhancement of the performance.
  • the formation by a centrifugal flow coating apparatus also has advantages that catalysts having a narrow distribution of particle size can be obtained and that, since said catalysts are particulate or spherical, the catalysts have high mechanical strength, little pressure loss and high resistance to friction and are easy to fill in or take out from a reaction apparatus.
  • centrifugal flow coating device is known as one method of forming particles from powder material.
  • Japanese Patent Publication No. 10878/1971 discloses said use with regard to a case where pharmaceutical compositions are sugar-coated.
  • Japanese Pat. Publication No. 17292/1977 also discloses it with regard to a case where particulate cores are coated with a catalyst and/or carriers.
  • this method is applied to the preparation of the above-mentioned oxide catalyst.
  • the process of this invention it is possible to easily obtain a spherical or particulate catalyst having the aforespecified surface area, pore volume and pore diameter distribution and having high physical strength by only using water as a binder or by optionally using, in combination therewith, a substance which imparts the catalyst with pores by combustion or volatilization at the time of firing.
  • the catalyst of this invention can be produced, for example, by charging an unfired catalyst material powder composition into a centrifugal flow coating apparatus to form particles with blowing heated air thereinto and spraying a binder such as water, taking out particles grown to the desired size in batchtype operation or in successive operation, then drying the particles as necessary and thereafter firing them at a temperature of 200 to 500° C., preferably 300° to 450° C.
  • the catalyst of this invention can be used directly as such, or by diluting it with an inert carrier or in the state in which the catalyst is held in said carrier.
  • an inert carrier In the formation of the particles, it is preferable to use, as a core, granules obtained by preforming a catalyst per se to a size more than 10 times larger than the particle size of the material powder.
  • an inert carrier can be also used as this core.
  • the inert carrier include silicon carbide, silica, alpha-alumina and others known as a refractory material.
  • a coating catalyst powder to grow a particle diameter it is preferable to preadjust the powder to not more than 100 mesh.
  • a polyvinyl alcohol, stearic acid, etc. may be added to the catalyst material powder composition at the time of preparing said composition or at the time of shaping.
  • a binder of the powder it is also possible to use water, ammonium nitrate, graphite, starch, etc, and organic solvents such as alcohol, acetone, etc., can be used as well.
  • Mo molybdenum
  • V vanadium
  • A represents at least one element selected from the group consisting of tungsten and niobium
  • B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony and thallium
  • C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals
  • D represents at least one element selected from the group consisting of silicon, aluminum and titanium
  • 0 oxygen
  • a catalytic gas phase oxidation reaction of this invention is carried out by introducing a material gas composed of 1 to 10% by volume of acrolein, 1 to 15% by volume of molecular oxygen, 5 to 60% by volume of water vapor and 20 to 80% by volume of an inert gas (e.g., a mixed gas consisting of nitrogen, carbonic acid gas, saturated hydrocarbon gas, etc. onto the catalyst at a temperature in the range of from 150° to 400 ° C. at a pressure of atmospheric pressure to 10 atm and at a space velocity of 500 to 20,000hr -1 (STP)
  • an acrolein-containing gas obtained by catalytic reaction of propylene may be also used directly.
  • a part of the suspension A was evaporated to dry solidness with stirring under heat. Then the resultant solid in the block state was dried in a drier at 120° C. for 5 hours, and milled to about 100 mesh to give a powder.
  • Alpha-alumina particles having an average diameter of 1 mm was first charged to a centrifugal flow coating apparatus. Then the above powder was charged thereto together with distilled water as a binder with blowing heated air at 90° C., and spherical particles having an average diameter of 5 mm were formed. The spherical particles obtained as above were fired at a temperature of 400° C. for 5 hours.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4.6) Cu.sub.(2.2) Cr.sub.(0.6) W.sub.(2.4).
  • This catalyst is referred to as a catalyst (I-1-1).
  • Example I-1-1 was repeated except that 40 wt. % ammonium nitrate aqueous solution was used as a binder in place of water, and a catalyst (I-1-2) was obtained.
  • a part of the suspension-A was evaporated to dry solidness with stirring under heat. Then the resultant solid in the block state was dried in a drier under air current at 120° C. for 5 hours, and the dried block was milled to not more than 100 mesh to give a powder. 2% by weight of a carbon powder was added to the powder, and the resultant mixture was formed into tablets having a diameter of 5 mm and height of 5 mm. The tablets were fired at 400° C. for 5 hours to prepare a catalyst (I-2-1). The same procedure was repeated to prepare another catalyst (I-2-2).
  • a part of the suspension-A was concentrated by evaporation until it could be extruded, and extruded so as to form extrudates having a diameter of 5 mm and length of 5 mm.
  • the extrudates were fired at 400° C. for 5 hours to prepare a catalyst (I-3-1).
  • the same procedure was repeated to prepare another catalyst (I-3-2).
  • a part of the suspension-A was subjected to concentrating heat treatment by external heat to concentrate it until it could be extruded.
  • the concentrate was extrusion-molded to form extrudates having a diameter of 6 mm and length of 4 to 7 mm.
  • the extrudates were subjected to a marmerizer to form 3 mm ⁇ 5 mm spheroids.
  • the spheroids were fired at 400° C. for 5 hours to prepare a catalyst (I-4).
  • a part of the suspension-A was evaporated to dry solidness with stirring under heat. Then the resultant solid in the block state was dried in a drier at 120° C. for 5 hours, and the dried block was milled to about 100 mesh to obtain a powder.
  • Alpha-alumina particles having an average diameter of 1 mm were charged first into a rolling particle-forming machine. And then the above powder was charged thereinto, and heated air at 80° C. and distilled water as a binder were used to form spheres having an average diameter of 5 mm. The spheres were fired at 400° C. for 5 hours to prepare a catalyst (I-5).
  • a part of the suspension-A was subjected to concentrating heat treatment by externally heating to obtain a soil-like substance, 50% by weight of which was dissipated when it was fired at 400° C.
  • the soil-like substance was formed by a pill-forming machine into spheres having an average diameter of 5 mm. The spheres were fired at 400° C. for 5 hours to prepare a catalyst (I-6).
  • Example I-1-1 An 8,000 hour-successive reaction test was carried out by the use of the catalyst of Example I-1-1.
  • the procedure for the reaction test was the same as in Example I.
  • the temperature in the beginning of the reaction was 200° C., however, it was sufficient to elevate the temperature by 5° C. during the period of time of 8,000 hours.
  • the reaction results at the reaction temperature of 205° C. were that the acrolein conversion ratio was 99.6% and the yield of acrylic acid in a single flow was 97.0%.
  • a part of the suspension-A was charged into an evaporator on a hot water bath, and added thereto was a particulate alpha-alumina carrier having a specific surface area of 1 m 2 /g, a porosity of 42%, a pore distribution, 92% of which was made by pores having diameters of 75 to 250 microns, and diameters of 3 to 5 mm.
  • the mixture was evaporated to dry solidness with stirring, and then fired at 400° C. for 5 hours to prepare a catalyst (I-7).
  • the reaction test was carried out in the same way as in Examples I-1 to I-6.
  • Table 1 shows physical properties and activities measured with regard to the catalysts I-1 to I-7.
  • a suspension was prepared in the same way as in Example 1 and divided into four equal portions for four batches. From these four batches, powders or clay-like substances were prepared as materials suitable for various forming methods. The materials, were formed into catalysts in the same way as in Examples I-1 to I-7 series, and the reproducibility in the same forming method was examined by comparing the performances. In the same forming method, catalysts of the four batches were prepared independently of one another in the same procedure and under the same conditions. The performance tests were carried out according to the procedure of Examples I-1 to I-7 series except that the test in Example II-1 was carried out according to Example I-1-1.
  • catalysts resulting from formation by centrifugal coating method have a smaller variation in values of physical property and high activity in catalyst performance, and it is seen on the basis of the smaller variation that the catalysts were prepared with good reproducibility.
  • the other formation methods in some batches give catalysts which do not have the surface area, pore volume and pore distribution specified by this invention, although the catalysts were prepared under the same conditions, and that, as method for obtaining catalysts having good performance with good reproducibility, these other forming methods are inferior to the centrifugal flow coating method.
  • suspension-B While 6.0 liters of water was heated with stirring, 234.0 g of ammonium metavanadate and 1,059.4 g of ammonium molybdate were dissolved in the water to prepare an aqueous solution. Separately, 241.6 g of copper nitrate and 40.4 g of ferric nitrate were dissolved in water to prepare another aqueous solution. These two aqueous solution were mixed. And further, added to the resulting solution was 134 ml of 20% by weight of SiO 2 -containing silica sol as a carrier to form a suspension. (The suspension is referred to as suspension-B.)
  • Example I-1-1 A part of the suspension-B was treated in the same way as in Example I-1-1 to prepare a catalyst. However, the firing was carried out at 400° C. for 6 hours.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4) Cu.sub.(2) Fe.sub.(0.2) Si.sub.(1.0).
  • a part of the suspension-B was treated in the same way as in Example I-2 to prepare catalysts. However, the firing was carried out at 400° C. for 6 hours.
  • Ammonium molybdate (1,596 g) was dissolved in 12 liters of water under heat. 220.8 g of ammonium metavanadate, 1,126.5 g of niobium hydroxide, 162 g of ferrous oxalate, 88.5 g of cuprous chloride and 45 g of potassium nitrate were consecutively added to the above solution with fully stirring. After the mixture was heated with stirring, 678 g of an SiO 2 powder was added to prepare a suspension. (This suspension is referred to as a suspension-C.)
  • Example I-1-1 A part of the suspension-C was treated in the same way as in Example I-1-1 to prepare a catalyst except that the firing was carried out at 420° C. for 5 hours.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(2.5) Nb.sub.(8.4) Cu.sub.(1.2) Fe.sub.(1.2) K.sub.(0.6) Si.sub.(15).
  • Example I-3 A part of the suspension-C was treated in the same way as in Example I-3 to prepare catalysts. However, the firing was carried out at 420° C. for 5 hours.
  • a suspension was obtained in the same way as in Example I. There were used antimony pentoxide as an antimony source, a nitrate as a magnesium source and an oxide as an aluminum source. (This suspension is referred to as a suspension-D.)
  • Example I-1-1 A part of the suspension-D was treated in the same way as in Example I-1-1 to prepare a catalyst.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4.0) Sb.sub.(0.5) Mg.sub.(2.0) Al.sub.(5.0).
  • a suspension was obtained in the same way as in Example I.
  • a cesium source and strontium source nitrates were used, and as a titanium source, an oxide was used. (This suspension is referred to as a suspension-E.)
  • Example I-1-1 A part of the suspension-E was treated in the same way as in Example I-1-1 to prepare a catalyst.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4) W.sub.(2.0) Cu.sub.(2.0) Sr.sub.(2.0) Ti.sub.(10).
  • a part of the suspension-E was formed into catalysts according to Example I-5.
  • a suspension was obtained in the same way as in Example I. Additionally used were ferric nitrate as an iron source, sodium nitrate as a sodium source and an oxide as an aluminum source. (This suspension is referred to as a suspension-F.)
  • Example I-1-1 A part of the suspension-F was treated in the same way as in Example I-1-1 to prepare a catalyst.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(8.0) W.sub.(4.0) Cu.sub.(1.0) Fe.sub.(1.0) Na.sub.(0.5) Al.sub.(5.0).
  • a part of the suspension-F was formed into catalysts according to Example I-6.
  • a suspension was obtained in the same way as in Example I. In addition, there were used nitrates as bismuth and rubidium sources and silica gel as a silicon source. (This suspension is referred to as a suspension-G).
  • Example I-1-1 A part of the suspension-G was treated in the same way as in Example I-1-1 to prepare a catalyst.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(8.0 W.sub.(4.0) Cu.sub.(1.0) Bi.sub.(1.0) Rb.sub.(0.05) Si.sub.(5.0).
  • a part of the suspension-G was formed into catalysts according to Example I-7.
  • a suspension was obtained in the same way as in Example I. In addition, there were used nitrates as bismuth and cesium sources and silica gel as a silicon source. (This suspension is referred to as a suspension-H).
  • Example I-1-1 A part of the suspension-H was treated in the same way as in Example I-1-1 to prepare a catalyst.
  • the compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(8.0) W.sub.(1.0) Bi.sub.(1.0) Cs.sub.(0.05) Si.sub.(5.0).
  • a part of the suspension-H was formed into catalysts according to Example I-2.
  • Example I-1-1 was repeated except that alpha-alumina particle having an average diameter of 3 mm was first charged to a centrifugal flow coating apparatus as a core in place of alpha-alumina particle having an average diameter of 1 mm.
  • Example X-1 was repeated except that alpha-alumina particle having an average diameter of 5 mm was first charged as a core.
  • Example X-2 By the use of the catalysts of Examples X-1 to X-2, the reaction was carried out in the same way as in Example I.
  • the reaction results at the reaction temperature of 210° C. were that the acrolein conversion ratio was 99 6% and the yield of acrylic acid in a single flow was 97.2% for Example X-1 and the acrolein conversion ratio was 99.4% and the yield of acrylic acid in a single flow was 97.3% for Example X-2.
  • Example X-1 surface area was 4.0 m 2 /g, and pore volume was 0.237 cc/g, and the ratio of pore volume consisting of pores having diameters in the range of from 10 to 100 ⁇ m, from 1 to less than 10 ⁇ m, from 0.1 to less than 1 ⁇ m to the entire pore volume were 22%, 20% and 48% respectively.
  • Example X-2 surface area was 2.5 m 2 /g, and pore volume was 0.185 cc/g, and the ratio of pore volume consisting of pores having diameters in the range of from 10 to 100 ⁇ m, from 1 to less than 10 ⁇ m, from 0.1 to less than 1 ⁇ m to the entire pore volume were 22%, 21% and 55% respectively.

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Abstract

A catalyst for use in the production of acrylic acid by catalytic gas phase oxidation of acrolein, comprising active substances represented by general formula
Mo.sub.(a) V.sub.(b) A.sub.(c) B.sub.(d) C.sub.(e) D.sub.(f) O.sub.(x)
wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony, and thallium, C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and O represents oxygen; and further, a, b, c, d, e, f and x represent atomic ratios of Mo, V, A, B, C, D, and O respectively, and when a=12, then b=2 to 14, c=0 to 12, d=0 to 6, e=0 to 6 and f=0 to 30 and x is a numerical value determined depending upon the oxidation states of the other elements, and characterized by having a specific surface area of 0.50 to 15.0 m2 /g, a pore volume of 0.10 to 0.90 cc/g and a pore diameter distribution in which the pore diameters are distributed concentratedly in the ranges of from 0.1 to less than 1.0 μm, from 1.0 to less than 10.0 μm and from 10.0 to 100 μm. The catalyst can be prepared, with good reproducibility, by charging an unfired catalyst material powder composition into a centrifugal flow coating apparatus to form particles having an average diameter of 2 to 10 mm, and then firing the particles.

Description

This invention relates to a catalyst suitable for the production of acrylic acid from acrolein, which comprises molybdenum and vanadium as essential components, and a process for the preparation thereof. More specifically, this invention relates to a catalyst for the oxidation of acrolein, which has high activity and excellent durability and which is characterized by specific properties, and a process for the preparation of said catalyst with ease and good reproducibility.
There are many literature articles proposing various catalysts for producing acrylic acid at high yields by a catalytic gas phase oxidation reaction of acrolein. These proposals are mainly concerned with selection of components for catalysts and proportions thereof. Some of them are also concerned with selection of catalyst properties and production processes with reproducibility. Although there are not a few proposals concerning catalyst properties such as surface area, pore volume, etc., none of these proposed catalysts are found to be on a satisfactory level.
For example, as a disclosure of the surface area, it is described in Japanese Laid-Open Patent Publications Nos. 86812/1973 and 91010/1973 that the catalyst surface areas of 0.1 to 50 m2 /g are preferable. However, those catalysts described therein have defects of high reaction temperatures and low level of performance. Japanese Laid-Open Patent Publications Nos. 47276/1974 and 24183/1975 describe that the specific surface areas of 0.1 to 8 m2 /g are preferable. However, those catalysts described therein also have a defect of high reaction temperatures as high as about 300° C. With regard to the definition of the pore volume and surface area, it is described in Japanese Laid-Open Patent Publications Nos. 65395/1974 and 62409/1974 that the surface areas of 4 to 8 m2 /g and pore volumes of 0.1 to 0.2 ml/g are preferable. However, those catalysts described therein comprise cobalt and molybdenum as active components and they are technically on a low level.
Japanese Laid-Open Patent Publication No. 47590/1976 describes that a catalyst comprising phosphorus, molybdenum and thallium or an element of Group IA or II of the periodic table and formed by rolling particle-forming method so as to have a surface area of 4 to 20 m2 /g and a pore volume of 0.08 to 0.5 ml/g has reproduction in performance. However, this catalyst also has defects that the reaction temperature is high and the performance is unsatisfactory. Japanese Laid-Open Patent Publication No. 9737/1982 discloses a catalyst comprising, as essential components, molybdenum, vanadium, copper, iron, manganese, alkali earth metal or zinc, and oxygen and further including phosphorus as an optional component, and a process for the production of acrylic acid by using said catalyst in the oxidation of acrolein. And it discloses an embodiment of the catalyst in which an alundum having a diameter of 3.5 mm is allowed to carry catalyst components by a rotatory sugar coater. In the catalyst therein, the reaction temperature is relatively low, i.e., about 200° C., and said catalyst achieves a high level in the yields. However, the catalyst obtained by the process has a problem in respect of reproducibility of its properties.
The present inventors have had an idea that the catalyst properties are not determined by the mere definition of catalyst surface area and/or pore volume but that industrially- excellent catalysts can be obtained only when the catalysts are imparted with properties resulting from the combination of three factors of catalyst surface area, pore volume and pore diameter distribution. Meanwhile, in the case of carrying out the oxidation reaction of acrolein by the use of a reaction apparatus having a fixed bed or moving bed, catalysts are used, in general, in the form of pellets having a suitable size. Such pellets are formed by using a tablet-forming machine, extruder, pill-forming machine, rolling particle-forming machine, etc. However, the physical property of the resultant catalyst is not constant, that is, most cases show poor reproducibility of catalyst performance. Thus, in such forming methods, it is difficult to obtain catalysts without lowering the catalyst performance.
Therefore, the present inventors made assiduous studies to clear up those variations of catalyst performance which are caused at the time of forming catalysts by using various forming machines. As a result, it was found that in the case of a catalyst material containing Mo, V, A, B, C, D, and 0 (wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony and thallium, C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and O represents oxygen,) as active components, the catalyst performance lowers to a great extent and the performance and physical property vary depending upon forming methods, and it was also found that the main cause of the foregoing is that since the pores of the catalyst are conditioned at the formation time, the catalyst surface area, pore volume and pore diameter are controlled.
Accordingly, further studies were made with regard to the surface area, pore volume and pore distribution in order to obtain a catalyst comprising the above components and having excellent performance. As a result, it was found that such a catalyst has to satisfy three conditions that it has a surface area of 0.50 to 15.0 m2 /g, that it has a pore volume of 0.10 to 0.90 cc/g and that it has a pore diameter distribution in which the pore diameters are distributed concentratedly in the ranges of from 0.1 to less than 1.0 μm, from 1.0 to less than 10.0 μm and from 10 to 100 μm. The pore volume composed of pores having pore diameters in the range of from 10 to less than 100 μm is not less than 10% of the entire pore volume, especially preferably, 15 to 40%, and the pore volumes composed of pores having pore diameters in the range of from 1.0 to less than 10.0 μm and pores having pore diameters in the range from 0.1 to 100 μm are not less than 10% of the entire pore volume respectively, especially preferably, 15 to 65 % respectively. It was found that when these conditions are satisfied, both of the activity and the selectivity of the above catalyst are enhanced that is, a pore having a smaller pore diameter, e.g., less than 1.0 μm, has a larger contribution toward the surface area and pore volume than pores having a larger pore diameters, e.g. larger than 0.1 μm. However, in the pores having a contribution toward the activity and selectivity to the effective reaction product, the mere larger proportion of the smaller pores is not sufficient. And if there is not a distribution in which pores are also distributed in two ranges of from 1.0 to less than 10.0 μm and from 10.0 to 100 μm, it is not possible to obtain enhancement of the performance.
On the basis of the above finding, the present inventors diligently continued the studies and consequently found that the use of a centrifugal flow coating apparatus in shaping of an unfired catalyst powder not formed into particles can give catalysts which are excellent in reproducibility and exhibit excellent catalyst performance.
In usual formation methods of catalysts, a rolling particle-forming method, marmerizer-forming method, fluidized bed particle-forming method, etc., are used for the preparation of spherical shapes, and an extrusion method, tablet-forming method, etc., are used for cylindrical shapes. However, in the case of using these formation methods, it is difficult in many cases to form catalysts without degrading the catalyst performance, the performance frequently varies widely and the reproducibility is often poor. In contrast thereto, in the use of a centrifugal flow coating apparatus according to this invention, the apparatus is simply operated and gives good reproducibility and it is possible to prepare spherical or particulate catalysts. Further, the formation by a centrifugal flow coating apparatus also has advantages that catalysts having a narrow distribution of particle size can be obtained and that, since said catalysts are particulate or spherical, the catalysts have high mechanical strength, little pressure loss and high resistance to friction and are easy to fill in or take out from a reaction apparatus.
Meanwhile, the use of a centrifugal flow coating device is known as one method of forming particles from powder material. For example, Japanese Patent Publication No. 10878/1971 discloses said use with regard to a case where pharmaceutical compositions are sugar-coated. Japanese Pat. Publication No. 17292/1977 also discloses it with regard to a case where particulate cores are coated with a catalyst and/or carriers.
In this invention, this method is applied to the preparation of the above-mentioned oxide catalyst. According to the process of this invention, it is possible to easily obtain a spherical or particulate catalyst having the aforespecified surface area, pore volume and pore diameter distribution and having high physical strength by only using water as a binder or by optionally using, in combination therewith, a substance which imparts the catalyst with pores by combustion or volatilization at the time of firing. The catalyst of this invention can be produced, for example, by charging an unfired catalyst material powder composition into a centrifugal flow coating apparatus to form particles with blowing heated air thereinto and spraying a binder such as water, taking out particles grown to the desired size in batchtype operation or in successive operation, then drying the particles as necessary and thereafter firing them at a temperature of 200 to 500° C., preferably 300° to 450° C.
The catalyst of this invention can be used directly as such, or by diluting it with an inert carrier or in the state in which the catalyst is held in said carrier. In the formation of the particles, it is preferable to use, as a core, granules obtained by preforming a catalyst per se to a size more than 10 times larger than the particle size of the material powder. Naturally, an inert carrier can be also used as this core. Examples of the inert carrier include silicon carbide, silica, alpha-alumina and others known as a refractory material. With regard to a coating catalyst powder to grow a particle diameter, it is preferable to preadjust the powder to not more than 100 mesh. In order to prepare a catalyst having the surface area, pore volume and pore diameter distribution specified by this invention with good reproducibility, for example, a polyvinyl alcohol, stearic acid, etc., may be added to the catalyst material powder composition at the time of preparing said composition or at the time of shaping. As a binder of the powder, it is also possible to use water, ammonium nitrate, graphite, starch, etc, and organic solvents such as alcohol, acetone, etc., can be used as well.
The chemical composition of the catalyst of this invention is known in itself and is represented by the following general formula
Mo.sub.(a) V.sub.(b) A.sub.(c) B.sub.(d) C.sub.(e) D.sub.(f) O.sub.(x)
(wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony and thallium C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and 0 represents oxygen; and further, a, b, c, d, e, f and x represent atomic ratios of Mo, V, A, B, C, D, and 0 respectively, and when a=12, then b=2 to 14, c=0 to 12, d=0 to 6, e=0 to 6 and f=0 to 30 and x is a numerical value determined depending upon the oxidation states of the other elements).
A catalytic gas phase oxidation reaction of this invention is carried out by introducing a material gas composed of 1 to 10% by volume of acrolein, 1 to 15% by volume of molecular oxygen, 5 to 60% by volume of water vapor and 20 to 80% by volume of an inert gas (e.g., a mixed gas consisting of nitrogen, carbonic acid gas, saturated hydrocarbon gas, etc. onto the catalyst at a temperature in the range of from 150° to 400 ° C. at a pressure of atmospheric pressure to 10 atm and at a space velocity of 500 to 20,000hr -1 (STP) In addition, as a material gas, an acrolein-containing gas obtained by catalytic reaction of propylene may be also used directly.
The following Examples and Comparative Examples illustrate this invention more in detail. However, this invention shall not be limited to these Examples. In this invention, the conversion ratio and the yield in a single flow are respectively defined as follows. ##EQU1##
EXAMPLE I (Preparation of suspension of catalyst material)
While 50 liters of water was stirred under heat, dissolved therein were 1,560 g of ammonium paratungstate, 1,290 g of ammonium metavanadate, 5,070 g of ammonium molybdate and 180 g of ammonium dichromate to prepare an aqueous solution. Separately, 1,290 g of copper nitrate was dissolved in 3.0 liters of water to prepare another aqueous solution. These two solutions were mixed, and the mixture solution was heated and stirred to give a suspension. (The suspension is referred to as a suspension-A.)
EXAMPLE I-1-1 (Preparation of a catalyst by a centrifugal flow coating method)
A part of the suspension A was evaporated to dry solidness with stirring under heat. Then the resultant solid in the block state was dried in a drier at 120° C. for 5 hours, and milled to about 100 mesh to give a powder. Alpha-alumina particles having an average diameter of 1 mm was first charged to a centrifugal flow coating apparatus. Then the above powder was charged thereto together with distilled water as a binder with blowing heated air at 90° C., and spherical particles having an average diameter of 5 mm were formed. The spherical particles obtained as above were fired at a temperature of 400° C. for 5 hours. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4.6) Cu.sub.(2.2) Cr.sub.(0.6) W.sub.(2.4). This catalyst is referred to as a catalyst (I-1-1).
EXAMPLE I-1-2 (Preparation of a catalyst by a centrifugal flow coating method)
Example I-1-1 was repeated except that 40 wt. % ammonium nitrate aqueous solution was used as a binder in place of water, and a catalyst (I-1-2) was obtained.
EXAMPLES I-2-1 and I-2-2 (Preparation of catalysts by tablet-forming method)
A part of the suspension-A was evaporated to dry solidness with stirring under heat. Then the resultant solid in the block state was dried in a drier under air current at 120° C. for 5 hours, and the dried block was milled to not more than 100 mesh to give a powder. 2% by weight of a carbon powder was added to the powder, and the resultant mixture was formed into tablets having a diameter of 5 mm and height of 5 mm. The tablets were fired at 400° C. for 5 hours to prepare a catalyst (I-2-1). The same procedure was repeated to prepare another catalyst (I-2-2).
EXAMPLES I-3-1 and I-3-2 (Preparation of a catalyst by extrusion method)
A part of the suspension-A was concentrated by evaporation until it could be extruded, and extruded so as to form extrudates having a diameter of 5 mm and length of 5 mm. The extrudates were fired at 400° C. for 5 hours to prepare a catalyst (I-3-1). The same procedure was repeated to prepare another catalyst (I-3-2).
EXAMPLES I-4 (Preparation of a catalyst by marmerizer-forming method)
A part of the suspension-A was subjected to concentrating heat treatment by external heat to concentrate it until it could be extruded. The concentrate was extrusion-molded to form extrudates having a diameter of 6 mm and length of 4 to 7 mm. Then the extrudates were subjected to a marmerizer to form 3 mm×5 mm spheroids. The spheroids were fired at 400° C. for 5 hours to prepare a catalyst (I-4).
EXAMPLE I-5 (Preparation of a catalyst by rolling particle-forming method)
A part of the suspension-A was evaporated to dry solidness with stirring under heat. Then the resultant solid in the block state was dried in a drier at 120° C. for 5 hours, and the dried block was milled to about 100 mesh to obtain a powder. Alpha-alumina particles having an average diameter of 1 mm were charged first into a rolling particle-forming machine. And then the above powder was charged thereinto, and heated air at 80° C. and distilled water as a binder were used to form spheres having an average diameter of 5 mm. The spheres were fired at 400° C. for 5 hours to prepare a catalyst (I-5).
EXAMPLE I-6 (Preparation of a catalyst by pill-forming method)
A part of the suspension-A was subjected to concentrating heat treatment by externally heating to obtain a soil-like substance, 50% by weight of which was dissipated when it was fired at 400° C. The soil-like substance was formed by a pill-forming machine into spheres having an average diameter of 5 mm. The spheres were fired at 400° C. for 5 hours to prepare a catalyst (I-6).
[Reaction Test]
The activity test on each of the above catalysts I-1 to I-6 was carried out in the following procedure.
1,000 ml of the catalyst was charged to a steel reaction tube having an internal diameter of 25.4 mm, and a mixture gas obtained by catalytic gas phase oxidation of industrial-use propylene (having a purity of not less than 95%) in the presence of a catalyst of a molybdenum/cobalt/tungsten oxide type was introduced thereinto to carry out the reaction at a reaction temperature of 200° to 250° C. and at a space velocity of 3,000 hr-1.The average composition of the mixture gas for the reaction was as follows.
______________________________________                                    
Acrolein            5.64% by volume                                       
Propylene + propane 0.65% by volume                                       
Acrylic acid + acetic acid                                                
                    0.74% by volume                                       
Nitrogen            70.03% by volume                                      
Water vapor         17.22% by volume                                      
Oxygen              4.75% by volume                                       
Others              0.97% by volume                                       
______________________________________
EXAMPLE I-1-3
An 8,000 hour-successive reaction test was carried out by the use of the catalyst of Example I-1-1. The procedure for the reaction test was the same as in Example I. The temperature in the beginning of the reaction was 200° C., however, it was sufficient to elevate the temperature by 5° C. during the period of time of 8,000 hours. The reaction results at the reaction temperature of 205° C. were that the acrolein conversion ratio was 99.6% and the yield of acrylic acid in a single flow was 97.0%.
EXAMPLE I-7 (Preparation of a catalyst on a carrier)
A part of the suspension-A was charged into an evaporator on a hot water bath, and added thereto was a particulate alpha-alumina carrier having a specific surface area of 1 m2 /g, a porosity of 42%, a pore distribution, 92% of which was made by pores having diameters of 75 to 250 microns, and diameters of 3 to 5 mm. The mixture was evaporated to dry solidness with stirring, and then fired at 400° C. for 5 hours to prepare a catalyst (I-7). The reaction test was carried out in the same way as in Examples I-1 to I-6.
Table 1 shows physical properties and activities measured with regard to the catalysts I-1 to I-7.
                                  TABLE 1                                 
__________________________________________________________________________
                                                   Yield of               
                                                   acrylic                
                    Surface                                               
                         Pore                                             
                             Pore     Reaction                            
                                             Acrolein                     
                                                   acid in                
Ex-                 area volume                                           
                             distribution                                 
                                      temperature                         
                                             conversion                   
                                                   a single               
ample                                                                     
    Forming method  m.sup.2 /g                                            
                         cc/g                                             
                             A*.sup.1                                     
                                B*.sup.2                                  
                                   C*.sup.3                               
                                      (°C.)                        
                                             ratio flow                   
__________________________________________________________________________
I-1-1                                                                     
    Centrifugal flow coating method                                       
                    4.7  0.250                                            
                             22 21 55 210    99.8  97.1                   
I-1-2                                                                     
    "               4.8  0.247                                            
                             23 22 54 200    99.6  97.5                   
I-2-1                                                                     
    Tablet-forming method                                                 
                    2.7  0.150                                            
                             -- 25 70 210    90.6  75.2                   
I-2-2                                                                     
    "               2.0  0.110                                            
                             -- 21 74 210    85.3  72.5                   
I-3-1                                                                     
    Extrusion method                                                      
                    3.5  0.170                                            
                             -- 30 68 210    92.4  84.1                   
I-3-2                                                                     
    "               3.2  0.163                                            
                             -- 35 60 210    89.8  82.6                   
I-4 Marmerizer-forming method                                             
                    3.7  0.160                                            
                             -- 31 65 210    90.1  83.3                   
I-5 Rolling particle forming method                                       
                    4.1  0.210                                            
                             6  30 60 210    94.8  90.1                   
I-6 Pill-forming method                                                   
                    4.7  0.220                                            
                             8  28 62 210    93.2  88.5                   
I-7 Carrier added-forming method                                          
                    1.50 0.180                                            
                             -- 40 55 210    87.4  87.0                   
__________________________________________________________________________
 *.sup.1 Ratio (%) of pore volume consisting of pores having diameters in 
 the range of from 10 to 100 μm to the entire pore volume. (The asteris
 in the other Tables means the same.)                                     
 *.sup.2 Ratio (%) of pore volume consisting of pores having diameters in 
 the range of from 1 to less than 10 μm to the entire pore volume. (The
 asterisk in the other Tables means the same.)                            
 *.sup.3 Ratio (%) of pore volume consisting of pores having diameters in 
 the range of from 0.1 to less than 1 μm to the entire pore volume. (Th
 asterisk in the other Tables means the same.)
EXAMPLE II (Preparation of a catalyst and test on reproducibility thereof)
A suspension was prepared in the same way as in Example 1 and divided into four equal portions for four batches. From these four batches, powders or clay-like substances were prepared as materials suitable for various forming methods. The materials, were formed into catalysts in the same way as in Examples I-1 to I-7 series, and the reproducibility in the same forming method was examined by comparing the performances. In the same forming method, catalysts of the four batches were prepared independently of one another in the same procedure and under the same conditions. The performance tests were carried out according to the procedure of Examples I-1 to I-7 series except that the test in Example II-1 was carried out according to Example I-1-1.
The results are shown in Table 2.
As is clear in Table 2, catalysts resulting from formation by centrifugal coating method have a smaller variation in values of physical property and high activity in catalyst performance, and it is seen on the basis of the smaller variation that the catalysts were prepared with good reproducibility. On the other hand, it is further seen that the other formation methods in some batches give catalysts which do not have the surface area, pore volume and pore distribution specified by this invention, although the catalysts were prepared under the same conditions, and that, as method for obtaining catalysts having good performance with good reproducibility, these other forming methods are inferior to the centrifugal flow coating method.
                                  TABLE 2                                 
__________________________________________________________________________
                                                    Yield of              
                                          Reaction                        
                                               Acrolein                   
                                                    acrylic               
                        Surface                                           
                             Pore                                         
                                 Pore     tempera-                        
                                               conver-                    
                                                    acid in               
Ex-                 Batch                                                 
                        area volume                                       
                                 distribution                             
                                          ture sion a single              
ample                                                                     
    Forming method  No. m.sup.2 /g                                        
                             cc/g                                         
                                 A*.sup.1                                 
                                    B*.sup.2                              
                                       C*.sup.3                           
                                          (°C.)                    
                                               ratio                      
                                                    flow                  
__________________________________________________________________________
II-1                                                                      
    Centrifugal flow coating method                                       
                    1   4.7  0.246                                        
                                 23 23 52 210  99.6 97.4                  
    "               2   4.8  0.252                                        
                                 23 20 54 210  99.7 97.3                  
    "               3   4.9  0.251                                        
                                 21 21 56 210  99.6 97.5                  
    "               4   4.6  0.251                                        
                                 24 22 52 210  99.5 97.4                  
II-2                                                                      
    Tablet-forming method                                                 
                    1   2.5  0.170                                        
                                 -- 20 77 210  89.8 76.7                  
    "               2   2.0  0.160                                        
                                 -- 23 76 210  87.1 74.9                  
    "               3   2.9  0.200                                        
                                 -- 29 68 210  92.0 77.4                  
    "               4   2.3  0.171                                        
                                 -- 27 72 210  90.3 75.5                  
II-3                                                                      
    Extrusion method                                                      
                    1   3.0  0.185                                        
                                 -- 31 66 210  90.7 83.4                  
    "               2   3.2  0.190                                        
                                 -- 30 65 210  89.8 84.4                  
    "               3   2.7  0.153                                        
                                 -- 25 74 210  86.1 80.9                  
    "               4   3.4  0.216                                        
                                 -- 42 56 210  95.2 87.1                  
II-4                                                                      
    Marmerizer-forming method                                             
                    1   3.3  0.186                                        
                                 -- 35 61 210  91.3 85.8                  
    "               2   3.5  0.211                                        
                                 -- 32 67 210  89.1 84.6                  
    "               3   2.6  0.200                                        
                                 -- 23 73 210  85.7 79.7                  
    "               4   2.9  0.217                                        
                                 -- 25 74 210  87.3 81.7                  
II-5                                                                      
    Rolling particle forming method                                       
                    1   4.8  0.230                                        
                                 6  31 60 210  95.2 90.7                  
    "               2   3.9  0.210                                        
                                 4  32 62 210  96.0 91.5                  
    "               3   4.3  0.189                                        
                                 3  25 71 210  97.3 92.0                  
    "               4   4.4  0.214                                        
                                 7  42 47 210  94.7 90.8                  
II-6                                                                      
    Pill-forming method                                                   
                    1   4.8  0.220                                        
                                 3  25 71 210  92.6 88.9                  
    "               2   5.1  0.217                                        
                                 4  27 65 210  94.7 90.9                  
    "               3   4.0  0.169                                        
                                 2  23 74 210  90.5 87.8                  
    "               4   4.6  0.182                                        
                                 7  31 61 210  91.7 85.3                  
II-7                                                                      
    Carrier added-forming method                                          
                    1   1.7  0.153                                        
                                 -- 41 58 210  86.2 84.5                  
    "               2   1.9  0.193                                        
                                 -- 57 40 210  93.1 89.4                  
    "               3   1.2  0.167                                        
                                 -- 40 59 210  87.3 85.9                  
    "               4   1.6  0.148                                        
                                 -- 51 47 210  85.1 82.8                  
__________________________________________________________________________
EXAMPLE III (Preparation of material suspension for catalyst)
While 6.0 liters of water was heated with stirring, 234.0 g of ammonium metavanadate and 1,059.4 g of ammonium molybdate were dissolved in the water to prepare an aqueous solution. Separately, 241.6 g of copper nitrate and 40.4 g of ferric nitrate were dissolved in water to prepare another aqueous solution. These two aqueous solution were mixed. And further, added to the resulting solution was 134 ml of 20% by weight of SiO2 -containing silica sol as a carrier to form a suspension. (The suspension is referred to as suspension-B.)
EXAMPLE III-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-B was treated in the same way as in Example I-1-1 to prepare a catalyst. However, the firing was carried out at 400° C. for 6 hours. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4) Cu.sub.(2) Fe.sub.(0.2) Si.sub.(1.0).
EXAMPLES III-2-1 and III-2-2 (Preparation of catalysts by tablet-forming method)
A part of the suspension-B was treated in the same way as in Example I-2 to prepare catalysts. However, the firing was carried out at 400° C. for 6 hours.
[Reaction test]
By the use of the catalysts of Examples III-1 to III-2, the reactions were carried out in the same way as in Example I, except that the reaction temperature was set at 230° C.
EXAMPLE IV (Preparation of material suspension for catalyst)
Ammonium molybdate (1,596 g) was dissolved in 12 liters of water under heat. 220.8 g of ammonium metavanadate, 1,126.5 g of niobium hydroxide, 162 g of ferrous oxalate, 88.5 g of cuprous chloride and 45 g of potassium nitrate were consecutively added to the above solution with fully stirring. After the mixture was heated with stirring, 678 g of an SiO2 powder was added to prepare a suspension. (This suspension is referred to as a suspension-C.)
Example IV-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-C was treated in the same way as in Example I-1-1 to prepare a catalyst except that the firing was carried out at 420° C. for 5 hours. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(2.5) Nb.sub.(8.4) Cu.sub.(1.2) Fe.sub.(1.2) K.sub.(0.6) Si.sub.(15).
EXAMPLES IV-2-1 and IV-2-2 (Preparation of catalysts by extrusion method)
A part of the suspension-C was treated in the same way as in Example I-3 to prepare catalysts. However, the firing was carried out at 420° C. for 5 hours.
[Reaction test]
By the use of the catalysts of Examples IV-1 to IV-2, the reactions were carried out in the same way as in Example I, except that the reaction temperature was set at 240° C.
EXAMPLE V (Preparation of material suspension for catalyst)
A suspension was obtained in the same way as in Example I. There were used antimony pentoxide as an antimony source, a nitrate as a magnesium source and an oxide as an aluminum source. (This suspension is referred to as a suspension-D.)
EXAMPLE V-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-D was treated in the same way as in Example I-1-1 to prepare a catalyst. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4.0) Sb.sub.(0.5) Mg.sub.(2.0) Al.sub.(5.0).
EXAMPLES V-2-1 and V-2-2 (Preparation of catalysts by marmerizer-forming method)
A part of the suspension-D was treated in the same way as in Example I-4 to prepare catalysts.
[Reaction test]
By the use of the catalysts of Examples V-1 to V-2, the reactions were carried out in the same way as in Example I, except that the reaction temperature was set at 240° C.
EXAMPLE VI (Preparation of material suspension for catalyst)
A suspension was obtained in the same way as in Example I. As a cesium source and strontium source, nitrates were used, and as a titanium source, an oxide was used. (This suspension is referred to as a suspension-E.)
EXAMPLE VI-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-E was treated in the same way as in Example I-1-1 to prepare a catalyst. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(4) W.sub.(2.0) Cu.sub.(2.0) Sr.sub.(2.0) Ti.sub.(10).
EXAMPLES VI-2-1 and VI-2-2 (Preparation of a catalyst by rolling particle-forming method)
A part of the suspension-E was formed into catalysts according to Example I-5.
[Reaction test]
By the use of the catalysts of Examples VI-1 to VI-2, the reactions were carried out in the same way as in Example I, except that the reaction temperature was set at 220° C.
EXAMPLE VII (Preparation of material suspension for catalyst)
A suspension was obtained in the same way as in Example I. Additionally used were ferric nitrate as an iron source, sodium nitrate as a sodium source and an oxide as an aluminum source. (This suspension is referred to as a suspension-F.)
EXAMPLE VII-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-F was treated in the same way as in Example I-1-1 to prepare a catalyst. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(8.0) W.sub.(4.0) Cu.sub.(1.0) Fe.sub.(1.0) Na.sub.(0.5) Al.sub.(5.0).
EXAMPLES VII-2-1 AND VII-2-2 (Preparation of a catalyst by pill-forming method)
A part of the suspension-F was formed into catalysts according to Example I-6.
[Reaction test]
By the use of the catalysts of Examples VII-1 to VII-2, the reactions were carried out in the same way as in Example I, except that the reaction temperature was set at 210° C.
EXAMPLE VIII (Preparation of material suspension for catalyst)
A suspension was obtained in the same way as in Example I. In addition, there were used nitrates as bismuth and rubidium sources and silica gel as a silicon source. (This suspension is referred to as a suspension-G).
EXAMPLE VIII-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-G was treated in the same way as in Example I-1-1 to prepare a catalyst. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(8.0 W.sub.(4.0) Cu.sub.(1.0) Bi.sub.(1.0) Rb.sub.(0.05) Si.sub.(5.0).
EXAMPLES VIII-2-1 AND VIII-2-2 (Preparation of a catalyst by carrier-added forming method)
A part of the suspension-G was formed into catalysts according to Example I-7.
[Reaction test]
By the use of the catalysts of Examples VIII-1 to VIII-2, the reactions were carried out in the same way as in Example I.
EXAMPLE IX (Preparation of material suspension for catalyst)
A suspension was obtained in the same way as in Example I. In addition, there were used nitrates as bismuth and cesium sources and silica gel as a silicon source. (This suspension is referred to as a suspension-H).
EXAMPLE IX-1 (Preparation of a catalyst by centrifugal flow coating method)
A part of the suspension-H was treated in the same way as in Example I-1-1 to prepare a catalyst. The compositional ratio of the elements except oxygen in the resultant catalyst oxide was Mo.sub.(12) V.sub.(8.0) W.sub.(1.0) Bi.sub.(1.0) Cs.sub.(0.05) Si.sub.(5.0).
EXAMPLES IX-2-1 ANDIX-2-2 (Preparation of a catalyst by tablet-forming method)
A part of the suspension-H was formed into catalysts according to Example I-2.
[Reaction test]
By the use of the catalysts of Examples IX-1 to IX-2, the reactions were carried out in the same way as in Example I.
The results of the above Examples III to IX are summarized in Table 3.
                                  TABLE 3                                 
__________________________________________________________________________
                                                    Yield of              
                                                    acrylic               
                     Surface                                              
                          Pore                                            
                              Pore     Reaction                           
                                              Acrolein                    
                                                    acid in               
Ex-                  area volume                                          
                              distribution                                
                                       temperature                        
                                              conversion                  
                                                    a single              
ample                                                                     
     Forming method  m.sup.2 /g                                           
                          cc/g                                            
                              A*.sup.1                                    
                                 B*.sup.2                                 
                                    C*.sup.3                              
                                       (°C.)                       
                                              ratio flow                  
__________________________________________________________________________
III-1                                                                     
     Centrifugal flow coating method                                      
                     5.0  0.283                                           
                              21 30 48 230    96.8  92.9                  
III-2-1                                                                   
     Tablet-forming method                                                
                     3.1  0.216                                           
                              -- 25 70 230    92.0  84.6                  
III-2-2                                                                   
     "               2.2  0.179                                           
                              -- 17 82 230    88.5  82.3                  
IV-1 Centrifugal flow coating method                                      
                     6.3  0.324                                           
                              18 33 48 240    94.3  90.5                  
IV-2-1                                                                    
     Extrusion method                                                     
                     4.1  0.261                                           
                              -- 42 57 240    91.7  85.5                  
IV-2-2                                                                    
     "               2.9  0.215                                           
                              -- 30 69 240    88.4  80.6                  
V-1  Centrifugal flow coating method                                      
                     4.1  0.305                                           
                              16 32 49 240    98.7  89.8                  
V-2-1                                                                     
     Marmerizer-forming method                                            
                     3.9  0.213                                           
                              -- 31 66 240    92.5  81.4                  
V-2-2                                                                     
     "               2.6  0.192                                           
                              -- 46 53 240    89.8  82.6                  
VI-1 Centrifugal flow coating method                                      
                     4.2  0.295                                           
                              19 27 50 220    99.6  95.6                  
VI-2-1                                                                    
     Rolling particle forming method                                      
                     4.7  0.281                                           
                              7  40 50 220    95.1  91.3                  
VI-2-2                                                                    
     "               3.6  0.325                                           
                              3  23 71 220    92.6  89.8                  
VII-1                                                                     
     Centrifugal flow coating method                                      
                     5.6  0.371                                           
                              23 34 40 220    99.1  95.5                  
VII-2-1                                                                   
     Pill-forming method                                                  
                     4.1  0.257                                           
                              3  21 71 220    93.4  89.7                  
VII-2-2                                                                   
     "               4.9  0.326                                           
                              9  18 69 220    96.7  90.9                  
VIII-1                                                                    
     Centrifugal flow coating method                                      
                     4.3  0.310                                           
                              35 20 41 210    97.8  94.9                  
VIII-2-1                                                                  
     Carrier added-forming method                                         
                     1.2  0.126                                           
                              -- 44 51 210    86.9  82.6                  
VIII-2-2                                                                  
     "               1.8  0.192                                           
                              -- 50 48 210    89.3  83.9                  
IX-1 Centrifugal flow coating method                                      
                     4.3  0.256                                           
                              21 29 49 210    97.9  94.0                  
IX-2-1                                                                    
     Tablet-forming method                                                
                     2.1  0.169                                           
                              -- 21 76 210    91.6  87.9                  
IX-2-2                                                                    
     "               3.3  0.217                                           
                              -- 30 68 210    94.3  88.9                  
__________________________________________________________________________
EXAMPLE X-1 (Preparation of catalyst by a centrifugal flow coating method)
Example I-1-1 was repeated except that alpha-alumina particle having an average diameter of 3 mm was first charged to a centrifugal flow coating apparatus as a core in place of alpha-alumina particle having an average diameter of 1 mm.
EXAMPLE X-2
Example X-1 was repeated except that alpha-alumina particle having an average diameter of 5 mm was first charged as a core.
[Reaction test]
By the use of the catalysts of Examples X-1 to X-2, the reaction was carried out in the same way as in Example I. The reaction results at the reaction temperature of 210° C. were that the acrolein conversion ratio was 99 6% and the yield of acrylic acid in a single flow was 97.2% for Example X-1 and the acrolein conversion ratio was 99.4% and the yield of acrylic acid in a single flow was 97.3% for Example X-2.
As for Example X-1, surface area was 4.0 m2 /g, and pore volume was 0.237 cc/g, and the ratio of pore volume consisting of pores having diameters in the range of from 10 to 100 μm, from 1 to less than 10 μm, from 0.1 to less than 1 μm to the entire pore volume were 22%, 20% and 48% respectively.
As for Example X-2, surface area was 2.5 m2 /g, and pore volume was 0.185 cc/g, and the ratio of pore volume consisting of pores having diameters in the range of from 10 to 100 μm, from 1 to less than 10 μm, from 0.1 to less than 1 μm to the entire pore volume were 22%, 21% and 55% respectively.

Claims (6)

What we claim is:
1. A catalyst for use in the production of acrylic acid by catalytic gas phase oxidation of acrolein, comprising active substances represented by general formula
wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony and thallium, C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and O represents oxygen; and further, a, b, c, d, e, f and x represents atomic ratios of Mo, V, A, B, C, D, and O respectively, and when a=12, then b=2 to 14, c=0 to 12, d? 0 to 6, e? 0 to 6 and f? 0 to 30 and x is a numerical value determined depending upon the oxidation states of the other elements, and said catalyst being prepared by charging an unfired catalyst material powder into a centrifugal flow coating apparatus to form particles, and firing the particles, wherein said particles are characterized by having a specific surface area of 0.50 to 15.0 m2 /g, a pore volume of 0.10 to 0.90 cc/g and a pore diameter distribution in which the pore diameters are distributed concentratedly in each of the ranges of from 0.1 to less than 1.0 μm, from 1.0 to less than 10.0 μm and from 10.0 to 100 μm.
2. A catalyst according to claim 1 wherein the pore volume composed of pores having pore diameters in the range of from 0.1 to less than 1.0 μm, the pore volume composed of pores having pore diameters in the range of from 1.0 to less than 10.0 μm and the pore volume composed of pores having pore diameters in the range of from 10 to 100 μm are each respectively at least 10% based on the entire pore volume.
3. A catalyst according to claim 1 wherein the pore volume composed of pores having pore diameters in the range of from 10 to less than 100 μm, the pore volume composed of pores having pore diameters in the range of from 1.0 to less than 10.0 μm and the pore volume composed of pores having pore diameters in the range of from 0.1 to 1.0 μm are respectively 15 to 40%, 15 to 65% and 15 to 65% based on the entire pore volume.
4. In a process for preparation, with good reproductibility, of a catalyst which is used in the production of acrylic acid by catalytic gas phase oxidation of acrolein and which comprises active substances represented by the general formula
Mo.sub.(a) V.sub.(b) A.sub.(c) B.sub.(d) C.sub.(e) D.sub.(f) O.sub.(x)
wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony and thallium, C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and O represents oxygen; and further, a, b, c, d, e, f and x represent atomic ratios of Mo, V, A, B, C, D, and O, respectively, and when a=12, then b=2 to 14, c=0 to 12, d=0 to 6, e=0 to 6 and f=0 to 30 and x is a numerical value determined depending upon the oxidation states of the other elements; the improvement comprising charging an unfired catalyst material powder composition into a centrifugal flow coating apparatus to form particles having an average diameter of 2 to 10 mm, and then firing the particles thereby to obtain the catalyst having a specific surface area of 0.50 to 15.0 m2 /g, a pore volume of 0.10 to 0.90 cc/g and a pore diameter distribution in which the pore diameters are distributed concentratedly in each of the ranges of from 0.1 to less than 1.0 μm, from 1.0 to less than 10.0 μm and from 10.0 to 100 μm.
5. A process according to claim 4 for the preparation of a catalyst in which the pore volume composed of pores having pore diameters in the range of from 0.1 to less than 1.0 μm, the pore volume composed of pores having pore diameters in the range of from 1.0 to less than 10.0 μm and the pore volume composed of pores having pore diameters in the range of from 10 to 100 μm are each respectively at least 10% based on the entire pore volume.
6. A process according to claim 4 for the preparation of a catalyst in which the pore volume composed of pores having pore diameters in the range of from 10 to less than 100 μm, the pore volume composed of pores having pore diameters in the range of from 1.0 to less than 10.0 μm and the pore volume composed of pores having pore diameters in the range of from 0.1 to 1.0 μm are respectively 15 to 40%, 15 to 65% and 15 to 65% based on the entire pore volume.
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CS274469B2 (en) 1991-04-11
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JPS6485139A (en) 1989-03-30
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RU1833201C (en) 1993-08-07
KR930007409B1 (en) 1993-08-10

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